Hydrocarbon conversion using UZM-53

ABSTRACT

A new crystalline aluminosilicate zeolite comprising a MTT framework has been synthesized that has been designated UZM-53. This zeolite is represented by the empirical formula:
 
M +   m R r Al 1-x E x Si y O z  
 
where M represents sodium, potassium or a combination of sodium and potassium cations, R is the organic structure directing agent or agents derived from reactants R1 and R2 where R1 is diisopropanolamine and R2 is a chelating diamine, and E is an element selected from the group consisting of gallium, iron, boron and mixtures thereof. Catalysts made from UZM-53 have utility in various hydrocarbon conversion reactions such as oligomerization.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Division of copending application Ser. No.15/798,375 filed Oct. 30, 2017, which is a Continuation of InternationalApplication No. PCT/US2016/039513 filed Jun. 27, 2016 which applicationclaims benefit of U.S. Provisional Application No. 62/186,924 filed Jun.30, 2015, the contents of which cited applications are herebyincorporated by reference in their entirety.

BACKGROUND OF THE INVENTION

This invention relates to a new aluminosilicate zeolite comprising a MTTframework designated UZM-53 and its use as a catalyst in hydrocarbonconversion processes. This zeolite is represented by the empiricalformula:M⁺ mRrAl1-xExSiyOzM⁺ _(m)R_(r)Al_(1-x)E_(x)Si_(y)O_(z)where M represents sodium, potassium or a combination of sodium andpotassium cations, R is the organic structure directing agent or agentsderived from reactants R1 and R2 where R1 is diisopropanolamine and R2is a chelating diamine, and E is an element selected from the groupconsisting of gallium, iron, boron and mixtures thereof. UZM-53 hasutility in various hydrocarbon conversion reactions such asoligomerization.

Zeolites are crystalline aluminosilicate compositions which aremicroporous and which are formed from corner sharing AlO₂ and SiO₂tetrahedra. Numerous zeolites, both naturally occurring andsynthetically prepared, are used in various industrial processes.Synthetic zeolites are prepared via hydrothermal synthesis employingsuitable sources of Si, Al and structure directing agents such as alkalimetals, alkaline earth metals, amines, or organoammonium cations. Thestructure directing agents reside in the pores of the zeolite and arelargely responsible for the particular structure that is ultimatelyformed. These species balance the framework charge associated withaluminum and can also serve as space fillers. Zeolites are characterizedby having pore openings of uniform dimensions, having a significant ionexchange capacity, and being capable of reversibly desorbing an adsorbedphase which is dispersed throughout the internal voids of the crystalwithout significantly displacing any atoms which make up the permanentzeolite crystal structure. Zeolites can be used as catalysts forhydrocarbon conversion reactions, which can take place on outsidesurfaces as well as on internal surfaces within the pore.

As used herein, zeolites may be referred to by proper name, such asZSM-23, or by structure type code, such as MTT. These three letter codesindicate atomic connectivity and hence pore size, shape and connectivityfor the various known zeolites. The list of these codes may be found inthe Atlas of Zeolite Framework Types, which is maintained by theInternational Zeolite Association Structure Commission athttp://www.iza-structure.org/databases/. The structure type MTT has beendescribed in the literature and is known to contain 1-dimensional10-ring channels normal to the c axis. Zeolites are distinguished fromeach other on the basis of their composition, crystal structure andadsorption properties. One method commonly used in the art todistinguish zeolites is x-ray diffraction.

Several related molecular sieves have been disclosed but there aresignificant differences between those molecular sieves and those of thepresent invention. Plank, Rosinski, and Rubin describe ZSM-23, the MTTtype material, in U.S. Pat. No. 4,076,842 as having a SiO₂/Al₂O₃ ratioof from 40-250 and preferably from 50-220. ZSM-23 is synthesized using anitrogen-containing organic cation. Valyocsik, describing an improvedmethod of synthesis of ZSM-23 in U.S. Pat. No. 4,490,342 describesZSM-23 as having a SiO₂/Al₂O₃ ratio of from 40-5000 and preferably from50-2000. ZSM-23 is synthesized using an organic cation of the formula(CH₃)₃N⁺—R₁-⁺N(CH₃)₃. The present invention involves a SiO₂/Al₂O₃ ratioof less than 60, preferably less than 50 and most preferably less than44 and is not synthesized using an organic nitrogen-containing cation.Attempts to synthesize ZSM-23 at a SiO₂/Al₂O₃ ratio of less than 50 ledto the formation of ZSM-35, a material of FER structure type asdisclosed in U.S. Pat. No. 4,016,245.

U.S. Pat. No. 4,837,000 discloses a crystalline silicate, ISI-4, with aspecific XRD pattern that is synthesized in the presence of relativelylarge amounts of ethylene glycol or monoethanolamine.

Parker and Bibby describe the synthesis of KZ-1 in ZEOLITES 1983, 3,8-11 from reactant compositions comprising pyrrolidine, dimethylamine or2-aminopropane ranging from a SiO₂/Al₂O₃ ratio of from 55-110 to give aproduct with a particular XRD pattern and typically having a BET surfacearea of about 160 m²/g. The present invention is made at lower Si/Al2ratios than KZ-1.

Di Renzo and coworkers describe in U.S. Pat. No. 5,314,674 the synthesisof a MTT zeolite with a particular XRD pattern in the absence of anynitrogenous organic agent and in the presence of ethanol. The UZM-53 ofthe instant invention is synthesized in the presence of two nitrogenousorganic agents and in the absence of ethanol.

Zones describes SSZ-32 in U.S. Pat. No. 5,053,373 in the as-synthesizedand anhydrous state as having a characteristic XRD pattern, a SiO₂/Al₂O₃ratio of from 20 to less than 40 and comprising an N-loweralkyl-N′-isopropyl-imidazolium cation such asN,N′-diisopropylimidazolium cation. As prepared, the SiO₂/Al₂O₃ ratio istypically from 25:1 to about 37:1 and can be increased by treating thezeolite with chelating agents or acids to extract aluminum from thezeolite lattice.

Zones and coworkers describe in U.S. Pat. No. 7,390,763 the preparationof SSZ-32X, a MTT zeolite of a certain XRD pattern and a SiO₂/Al₂O₃ratio of from 20 to less than 40 and preferably from 30 to 35 andcomprising, in the as-synthesized and anhydrous form, an N-loweralkyl-N′-isopropyl-imidazolium cation such asN,N′-diisopropylimidazolium cation and an alkylamine such asisobutylamine.

Burton and Zones describe a process for preparing MTT zeolites and MTTzeolite compositions in U.S. Pat. No. 7,157,075 where the MTT zeolitessynthesized have a composition in the as-synthesized and anhydrous statewith a SiO₂/Al₂O₃ ratio of greater than 15, a ratio of at least onenitrogen-containing organic compound selected from a group includingN,N,N′,N′-tetramethylpropanediamine to SiO₂ of from 0.02 to 0.10 and aratio of alkali metal cation (or alkaline earth cation or mixturesthereof) to SiO₂ of from 0.015 to 0.1.

Nakagawa discloses in U.S. Pat. No. 5,707,601 processes for synthesizingMTT zeolites such as SSZ-32 utilizing small amines such as isobutylamineas the organic structure directing agent. These MTT zeolites havespecific XRD patterns and compositions different from those of theinstant invention.

Rouleau and coworkers describe in U.S. Pat. No. 6,475,464 an MTT zeoliteand process for preparing said zeolite wherein the synthesis is carriedout using at least one alkylated polymethylene α-ω diammonium derivativeand seeds of a zeolitic material different from the MTT zeolite to beprepared. The present invention does not utilize a diammonium compound,nor are seeds of a framework other than MTT used to crystallize theinstant zeolite.

Barri describes in GB2190910 the synthesis of a product they call ZSM-23from the crystallization of a gel comprising diisopropanolamine andhaving a SiO₂/Al₂O₃ ratio of greater than 50 and preferably in the rangefrom 60 to 500. The present invention involves a SiO₂/Al₂O₃ ratio ofless than 60, preferably less than 50 and most preferably less than 44.

SUMMARY OF THE INVENTION

A new material, UZM-53, has been made comprising a MTT framework thathas utility in hydrocarbon processes. The present invention relates tozeolite UZM-53, the process of making it and its use as a catalyst inhydrocarbon conversion processes. This zeolite is represented by theempirical formula:M⁺ _(m)R_(r)Al_(1-x)E_(x)Si_(y)O_(z)where M represents sodium, potassium or a combination of sodium andpotassium exchangeable cations, “m” is the mole ratio of M to (Al+E) andvaries from about 0.05 to about 1, R is the organic structure directingagent or agents derived from reactants R1 and R2 where R1 isdiisopropanolamine and R2 is a chelating diamine, “r” is the mole ratioof N from the organic structure directing agent or agents to (Al+E) andhas a value of from about 0.4 to about 1.5, E is an element selectedfrom the group consisting of gallium, iron, boron and mixtures thereof,“x” is the mole fraction of E and has a value from 0 to about 1.0, “y”is the mole ratio of Si to (Al+E) and varies from greater than 12 toabout 30 and “z” is the mole ratio of 0 to (Al+E) and has a valuedetermined by the equation: z=(m+r1+r2+3+4·y)/2. The zeolite UZM-53 hasa framework of MTT type. It may be present in the catalyst as unmodifiedzeolite UZM-53 or as UZM-53 modified zeolite. The UZM-53 containingcatalyst may take one of several forms, including for example, aspherical oil-dropped catalyst or an extruded catalyst. As stated, thepresent invention relates to a new aluminosilicate zeolite designatedUZM-53 that comprises a MTT framework. In a particular embodiment thezeolite designated as UZM-53 is characterized in that the as synthesizedmaterial has an x-ray diffraction pattern having at least thed-spacing's and intensities set forth in Table A.

TABLE A 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56W 16.32 5.43 W 18.18 4.88 W—M 19.72 4.50 S 20.04 4.43 W—M 21.00 4.23 S21.50 4.13 W—M 22.90 3.88 VS 24.10 3.69 VS 24.62 3.61 S 25.34 3.51 M—S26.02 3.42 W 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52 M—S

After the UZM-53 material was calcined, the x-ray diffraction patternshown in Table B was observed.

TABLE B 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56W 16.32 5.43 W 18.18 4.88 W 19.72 4.50 VS 20.04 4.43 W—M 21.00 4.23 S21.50 4.13 W 22.90 3.88 S 24.10 3.69 S 24.62 3.61 M 25.34 3.51 M 26.023.42 M 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52 M

Another aspect of the invention is a process of making the material froma low flammability reaction mixture comprising diisopropanolamine (DTPA)and a chelating diamine. Solutions of diisopropanolamine are highlypreferred.

Yet another embodiment of the invention is a hydrocarbon conversionprocess using the zeolite of the present invention. The processcomprises contacting the hydrocarbon with the zeolite at conversionconditions to give a converted hydrocarbon product. The hydrocarbonconversion processes include oligomerization, hydrocracking,hydroisomerization, hydrotreating, hydrodenitrogenation,hydrodesulfurization, naphthene ring opening, paraffin isomerization,olefin isomerization, conversion of an aromatic molecule to anotheraromatic molecule, polyalkylbenzene isomerization, disproportionation ofalkylbenzenes, aromatic alkylation, paraffin alkylation, paraffincracking, naphthene cracking, reforming, hydrogenation, dehydrogenation,transalkylation, dealkylation, hydration, and dehydration.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is an XRD pattern of the UZM-53 zeolite formed in Example 1. Thispattern shows the UZM-53 zeolite in the as-synthesized form.

FIG. 2 is also an XRD pattern of the UZM-53 zeolite formed in Example 1.This pattern shows the UZM-53 zeolite after calcination.

FIG. 3 is an XRD pattern of the MTT zeolite formed in ComparativeExample 3. This pattern shows the MTT zeolite after calcination.

FIG. 4 shows the UZM-53 product formed in Example 6. This pattern showsthe UZM-53 zeolite in the as-synthesized form.

FIG. 5 shows the ¹³C NMR spectrum obtained of the mother liquor fromExample 6 showing the presence of two organic structure directingagents.

FIG. 6 shows the XRD pattern of the UZM-53 zeolite of Example 6 in thecalcined form.

FIG. 7 shows a SEM photo of the Example 6 UZM-53 product at 100 nmresolution.

FIG. 8 shows hydrocarbon conversion in the form of olefinoligomerization from use of the UZM-53 zeolite catalyst as described inExample 11.

DETAILED DESCRIPTION OF THE INVENTION

Applicants have prepared an aluminosilicate zeolite whose topologicalstructure comprises an MTT framework as described in ATLAS OF ZEOLITEFRAMEWORK TYPES, which is maintained by the International ZeoliteAssociation Structure Commission athttp://www.iza-structure.org/databases/. This new zeolite has beendesignated as UZM-53. As will be shown in detail, UZM-53 is differentfrom the known zeolites in a number of its characteristics and findsutility as a catalyst in hydrocarbon conversion processes.

UZM-53 is represented in the as synthesized and anhydrous basis by theempirical formula:M⁺ _(m)R_(r)Al_(1-x)E_(x)Si_(y)O_(z)where M represents sodium, potassium or a combination of sodium andpotassium exchangeable cations, “m” is the mole ratio of M to (Al+E) andvaries from about 0.05 to about 1, R is the organic structure directingagent or agents derived from reactants R1 and R2 where R1 isdiisopropanolamine and R2 is a chelating diamine such astetramethylpropanediamine, “r” is the mole ratio of N from the organicstructure directing agent or agents to (Al+E) and has a value of fromabout 0.4 to about 1.5, E is an element selected from the groupconsisting of gallium, iron, boron and mixtures thereof, “x” is the molefraction of E and has a value from 0 to about 1.0, “y” is the mole ratioof Si to (Al+E) and varies from greater than 12 to about 30 and “z” isthe mole ratio of O to (Al+E) and has a value determined by theequation: z=(m+3+4·y)/2 and is characterized in that it has an x-raydiffraction pattern having at least the d-spacing's and intensities setforth in Table A.

TABLE A 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56W 16.32 5.43 W 18.18 4.88 W—M 19.72 4.50 S 20.04 4.43 W—M 21.00 4.23 S21.50 4.13 W—M 22.90 3.88 VS 24.10 3.69 VS 24.62 3.61 S 25.34 3.51 M—S26.02 3.42 W 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52 M—S

In an embodiment, “m” may vary from about 0.05 to about 0.75 or may varyfrom about 0.1 to about 0.5. In an embodiment, “y” may be greater than12 or greater than 15 or greater than 17 or less than 25 or less thanabout 22 or less than about 20. In an embodiment, when M represents acombination of sodium and potassium cations, the ratio of Na⁺/K⁺ in M⁺is in the range 0.10 to 2, and is preferably in the range of about 0.2to about 0.9. The ratio of Na⁺/K⁺ may be in the range from about 0.2 toabout 0.75. In an embodiment, “r” has a value of from about 0.9 to about1.4.

A chelating diamine is a di-tertiary amine of the formula(R3)(R4)N(R7)N′(R5)(R6) where R3, R4, R5 and R6 are independentlyselected from an alkyl group having the formula C_(n)H_(2n+1), where nis in the range from 1 to 4, R7 is an alkyl group having the formulaC_(p)H_(2p), where p is in the range from 2 to 6 and is connected to theN and N′ atoms at positions x and y of the alkyl chain where x and y areindependently selected from 1 to p, and where the total number of carbonatoms in the chelating diamine is in the range from 6 to 10. In anembodiment, n is 1 for at least two of R3, R4, R5 and R6. In anembodiment, at least two of R3, R4, R5 and R6 are CH₃. In an embodiment,R3, R4, R5 and R6 are equivalent. In an embodiment, R3, R4, R5 and R6are equivalent and n is 1. In an embodiment, p is in the range from 3 to5. In an embodiment, p is 3 and x and y are 1 and 3 respectively. In anembodiment, n is 1 for at least two of R3, R4, R5 and R6, p is 3 and xand y are 1 and 3 respectively. In an embodiment, R3, R4, R5 and R6 areequivalent, n is 1, p is 3 and x and y are 1 and 3 respectively. In anembodiment, the chelating diamine is tetramethylpropanediamine.

The UZM-53 material may be made from a low flashpoint reaction mixturehaving a composition expressed in terms of mole ratios of the oxides of:

-   -   aM₂O:bMX:cR1:dR2:1-eAl₂O₃:eE₂O₃:fSiO₂:gH₂O.

In an embodiment, the mixture that is used to make the UZM-53 contains

-   -   20Si:1Al(OH)₃:0.67NaOH:0.67KOH:6.26DIPA:1.266TMPDA:271H₂O        where M represents sodium, potassium or a combination of sodium        and potassium cations, “a” has a value from about 0.4 to about        3, MX represents a halide salt of sodium, potassium or a        combination of sodium and potassium cations, “b” has a value        from 0 to about 12, R1 is diisopropanolamine, “c” has a value of        about 8 to about 20, R2 is a chelating diamine, “d” has a value        of about 0.0 to about 2, E is an element selected from the group        consisting of gallium, iron, boron and mixtures thereof, “e” has        a value from 0 to about 1.0, “f” has a value from greater than        30 to about 60 and “g” has a value from about 300 to about 2000.        In an embodiment, “b” may be greater than 0 or greater than 0.5        or greater than about 1 or greater than about 2 or greater than        about 3 or greater than about 4 or greater than about 5 or less        than about 12 or less than about 10 or less than about 9 or less        than about 8 or less than about 7 or combinations thereof. In an        embodiment, “d” may be less than 1 or less than 0.50 or less        than 0.40. In an embodiment, “f” may be less than about 50. The        process may further comprise adding UZM-53 seeds to the reaction        mixture. Sources of M include but are not limited to sodium        hydroxide, potassium hydroxide, sodium aluminate, potassium        aluminate, sodium silicate, and potassium silicate. Sources of        MX include sodium chloride, sodium bromide, sodium iodide,        potassium chloride, potassium bromide, and potassium iodide. In        an embodiment, the source of MX is selected from the group        consisting of sodium chloride, potassium chloride and        combinations thereof. Sources of R1 can include aqueous        solutions, liquid or solid diisopropanolamine or combinations        thereof. Solutions of diisopropanolamine are highly preferred.        Diisopropanolamine is a low melting (approximately 40° C.) solid        which is not easily handled. The IUPAC name is        1-(2-hydroxypropylamino)propan-2-ol. The material either needs        to be chipped out of a container or melted and then handled as a        liquid, but it readily refreezes unless it is kept at higher        than room temperature. However, solutions of DIPA are stable and        readily prepared by melting the material and adding water while        stirring to make an aqueous solution. The concentration of the        R1 solution may be about 50 wt % or may be in the range from        about 10 wt % to about 90 wt % or may be in the range from 30 wt        % to about 70 wt % or may be in the range from about 40 wt % to        about 60 wt %. These solutions may then be easily used in the        synthesis. The source of E is selected from the group consisting        of alkali borates, boric acid, precipitated gallium        oxyhydroxide, gallium sulfate, ferric sulfate, ferric chloride        and mixtures thereof. The sources of aluminum include but are        not limited to aluminum alkoxides, precipitated aluminas,        aluminum metal, aluminum hydroxide, sodium aluminate, potassium        aluminate, aluminum salts and alumina sols. Specific examples of        aluminum alkoxides include, but are not limited to aluminum        sec-butoxide and aluminum ortho isopropoxide. Sources of silica        include but are not limited to tetraethylorthosilicate,        colloidal silica, fumed silica, precipitated silica and alkali        silicates.

In an embodiment, the reaction mixture is a low flammability reactionmixture. The flashpoint of a reaction mixture can be determined by ASTMD93 Standard Test Methods for Flash Point by Pensky-Martens Closed CupTester. In an aspect, a low flammability reaction mixture is one with aflashpoint greater than 50° C. or greater than 60° C. or greater than75° C. Higher values of the flashpoint by ASTM D93 indicate lowerflammability. The reaction mixture is reacted at a temperature of about150° to about 185° C. for a time of about 1 day to about 3 weeks in astirred, sealed reaction vessel under autogenous pressure. Aftercrystallization is complete, the solid product is isolated from theheterogeneous mixture by means such as filtration or centrifugation, andthen washed with deionized water and dried in air at ambient temperatureup to about 100° C. Preferably, the reaction mixture is reacted at atemperature of about 165° to about 175° C. for a time of about 1 day toabout 3 weeks. In an embodiment, the reaction mixture is reacted at atemperature of about 165° to about 175° C. for a time of about 1 day toabout 1 week.

UZM-53, in the as-synthesized and anhydrous basis, is characterized bythe x-ray diffraction pattern, having at least the d-spacings andrelative intensities set forth in Table 1 below. Those peakscharacteristic of UZM-53 are shown in Table 1. Additional peaks,particularly those of very weak intensity, may also be present. Allpeaks of medium or higher intensity present in UZM-53 are represented inTable 1. Diffraction patterns herein were obtained using a typicallaboratory powder diffractometer, utilizing the K_(α) line of copper; CuK alpha. From the position of the diffraction peaks represented by theangle 2theta, the characteristic interplanar distances d_(hkl) of thesample can be calculated using the Bragg equation. The intensity iscalculated on the basis of a relative intensity scale attributing avalue of 100 to the line representing the strongest peak on the X-raydiffraction pattern, and then: weak (w) means less than 15; weak tomedium (w-m) means in the range 8 to 35; medium (m) means in the range15 to 50; medium to strong (m-s) means in the range 35 to 60; strong (s)means in the range 50 to 90; very strong (vs) means more than 80.Intensities may also be shown as inclusive ranges of the above. TheX-ray diffraction patterns from which the data (d spacing and intensity)are obtained are characterized by a large number of reflections some ofwhich are broad peaks or peaks which form shoulders on peaks of higherintensity. Some or all of the shoulders may not be resolved. This may bethe case for samples of low crystallinity, of particular morphologicalstructures or for samples with crystals which are small enough to causesignificant broadening of the X-rays. This can also be the case when theequipment or operating conditions used to produce the diffractionpattern differ significantly from those used in the present case.

TABLE A 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56W 16.32 5.43 W 18.18 4.88 W—M 19.72 4.50 S 20.04 4.43 W—M 21.00 4.23 S21.50 4.13 W—M 22.90 3.88 VS 24.10 3.69 VS 24.62 3.61 S 25.34 3.51 M—S26.02 3.42 W 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52 M—S

In an embodiment, the peak at d=3.88 Å is the strongest peak. In anembodiment, two peaks of very strong intensity are present. In anembodiment, only two peaks of very strong intensity are present. In anembodiment, three peaks of strong intensity are present. As will beshown in detail in the examples, the UZM-53 material is thermally stableup to a temperature of at least 600° C. and in another embodiment, up toat least 800° C. Also as shown in the examples, the UZM-53 material mayhave a micropore volume as a percentage of total pore volume of lessthan 70% or less than 60% or less than 55% as determined by BET analysisusing N₂.

As synthesized, the UZM-53 material will contain some exchangeable orcharge balancing cations in its pores. These exchangeable cations can beexchanged for other cations, or in the case of organic SDAs, they can beremoved by heating under controlled conditions. It may be possible toremove some organic SDAs from the UZM-53 zeolite directly by ionexchange. The UZM-53 zeolite may be modified in many ways to tailor itfor use in a particular application. Modifications include calcination,ion-exchange, steaming, various acid extractions, ammoniumhexafluorosilicate treatment, or any combination thereof, as outlinedfor the case of UZM-4M in U.S. Pat. No. 6,776,975 B1 which isincorporated by reference in its entirety. Conditions may be more severethan shown in U.S. Pat. No. 6,776,975. Properties that are modifiedinclude porosity, adsorption, Si/Al ratio, acidity, thermal stability,and the like.

After calcination and on an anhydrous basis, the microporous crystallinezeolite UZM-53 has a three-dimensional framework of at least AlO₂ andSiO₂ tetrahedral units and an empirical composition in the hydrogen formexpressed by an empirical formula ofM1_(a′)N⁺Al_((1-x′))E_(x′)Si_(y′)O_(z″)where M1 is at least one exchangeable cation selected from the groupconsisting of alkali, alkaline earth metals, rare earth metals, ammoniumion, hydrogen ion and combinations thereof, “a” is the mole ratio of M1to (Al+E) and varies from about 0.05 to about 1, “N” is the weightedaverage valence of M1 and has a value of about +1 to about +3, E is anelement selected from the group consisting of gallium, iron, boron, andcombinations thereof, x′ is the mole fraction of E and varies from 0 to1.0, y′ is the mole ratio of Si to (Al+E) and varies from greater thanabout 12 to about 30 and z″ is the mole ratio of 0 to (Al+E) and has avalue determined by the equation:z″=(a·N+3+4·y′)/2.

In an embodiment, “a′” may vary from about 0.05 to about 0.75 or mayvary from about 0.1 to about 0.5. In an embodiment, “y′” may be greaterthan 12 or greater than 15 or greater than 17 or less than 25 or lessthan about 22 or less than about 20. In an embodiment, when M1 comprisesa combination of sodium and potassium cations, the molar ratio of Na⁺/K⁺in M1⁺ is in the range 0.10 to 2, and is preferably in the range ofabout 0.2 to about 0.9. The molar ratio of Na⁺/K⁺ may be in the rangefrom about 0.2 to about 0.75. In the calcined form, UZM-53 displays theXRD pattern shown in Table B. Those peaks characteristic of UZM-53 areshown in Table B. Additional peaks, particularly those of very weakintensity, may also be present. All peaks of medium or higher intensitypresent in UZM-53 are represented in Table B.

TABLE B 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56W 16.32 5.43 W 18.18 4.88 W 19.72 4.50 VS 20.04 4.43 W—M 21.00 4.23 S21.50 4.13 W 22.90 3.88 S 24.10 3.69 S 24.62 3.61 M 25.34 3.51 M 26.023.42 M 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52 M

The intensity is calculated on the basis of a relative intensity scaleattributing a value of 100 to the line representing the strongest peakon the X-ray diffraction pattern, and relative intensities are describedabove. In an embodiment, the peak at d=4.5 Å is the strongest peak. Inan embodiment, only one peak of very strong intensity is present. In anembodiment, 3 peaks of strong intensity are present.

In specifying the proportions of the zeolite starting material oradsorption properties of the zeolite product and the like herein, the“anhydrous state” of the zeolite will be intended unless otherwisestated. The term “anhydrous state” is employed herein to refer to azeolite substantially devoid of both physically adsorbed and chemicallyadsorbed water.

The crystalline UZM-53 zeolite of this invention can be used forseparating mixtures of molecular species, removing contaminants throughion exchange and catalyzing various hydrocarbon conversion processes.Separation of molecular species can be based either on the molecularsize (kinetic diameter) or on the degree of polarity of the molecularspecies. The separation process may comprise contacting at least twocomponents with the UZM-53 zeolite material to generate at least oneseparated component.

The UZM-53 zeolite of this invention can also be used as a catalyst orcatalyst support in various hydrocarbon conversion processes. Thecatalyst may contain from about 0 wt % or about 10 wt % to about 80 wt %or about 100 wt % of the UZM-53 zeolite. Hydrocarbon conversionprocesses are well known in the art and include oligomerization,hydrocracking, hydroisomerization, hydrotreating, hydrodenitrogenation,hydrodesulfurization, naphthene ring opening, paraffin isomerization,olefin isomerization, conversion of an aromatic molecule to anotheraromatic molecule, polyalkylbenzene isomerization, disproportionation ofalkylbenzenes, aromatic alkylation, paraffin alkylation, paraffincracking, naphthene cracking, reforming, hydrogenation, dehydrogenation,transalkylation, dealkylation, hydration, and dehydration.

Using a UZM-53 catalyst composition which contains a hydrogenationpromoter such as platinum or palladium, heavy petroleum residual stocks,cyclic stocks and other hydrocrackable charge stocks can be hydrocrackedat temperatures in the range of about 204° C. to about 649° C. (400° to1200° F.) or about 316° C. to about 510° C. (600° F. and 950° F.).Nickel, cobalt, molybdenum and tungsten are additionally known in theart as hydrogenation promoters. Reaction pressures are in the range ofatmospheric to about 24,132 kPa g (3,500 psig), or between about 1379 toabout 20,685 kPa g (200 to 3000 psig). Contact times usually correspondto liquid hourly space velocities (LHSV) in the range of about 0.1 hr⁻¹to 15 hr⁻¹%, preferably between about 0.2 and 10 hr⁻¹. Hydrogencirculation rates are in the range of 178 to about 8,888 std. m³/m³(1,000 to 50,000 standard cubic feet (scf) per barrel of charge), orabout 355 to about 5,333 std. m³/m³ (about 2,000 to about 30,000 scf perbarrel of charge). Suitable hydrotreating conditions are generallywithin the broad ranges of hydrocracking conditions set out above.

These same catalysts, i.e. those containing hydrogenation promoters, arealso useful in hydroisomerization processes in which feedstocks such asnormal paraffins are converted to saturated branched chain isomers.Hydroisomerization is carried out at a temperature of from about 93° C.to about 450° C. (200° F. to 842° F.), preferably about 150° C. to about300° C. (300° F. to 572° F.) with an LHSV value of from about 0.2 to1.0. Hydrogen is supplied to the reactor in admixture with thehydrocarbon feedstock in molar proportions (H₂/HC) of between 1 and 5.

Catalytic cracking processes are preferably carried out with the UZM-53composition using feedstocks such as gas oils, heavy naphthas,deasphalted crude oil residua, etc. with gasoline being the principaldesired product. Temperature conditions of about 454° C. to about 593°C. (about 850° F. to about 1100° F.), LHSV values of 0.5 to 10 andpressure conditions of from about 0 to about 344 kPa g (about 0 to 50psig) are suitable.

Alkylation of aromatics usually involves reacting an aromatic (C₂ toC₁₂), especially benzene, with a monoolefin to produce a linear alkylsubstituted aromatic. The process is carried out at an aromatic: olefin(e.g., benzene:olefin) ratio of between 1:1 and 30:1, a olefin LHSV ofabout 0.3 to about 10 hr⁻¹, a temperature of about 100° to about 250° C.and pressures of about 1379 kPa g to about 6895 kPa g (about 200 toabout 1000 psig). Further details on apparatus may be found in U.S. Pat.No. 4,870,222 which is incorporated by reference.

Alkylation of isoparaffins with olefins to produce alkylates suitable asmotor fuel components is carried out at temperatures of −30° to 40° C.,pressures from about atmospheric to about 6,895 kPa (1,000 psig) and aweight hourly space velocity (WHSV) of 0.1 to about 120. Details onparaffin alkylation may be found in U.S. Pat. No. 5,157,196 and U.S.Pat. No. 5,157,197, which are incorporated by reference.

Isomerization reactions are carried out under conditions identified forthe feedstock. Olefins are preferably isomerized at temperatures ofabout 150° C. to about 500° C. (302° F.-932° F.), while paraffins,naphthenes and alkyl aromatics are isomerized at temperatures of fromabout 350° C. to about 550° C. (662° F.-1022° F.). Particularlydesirable isomerization reactions contemplated herein include theconversion of n-heptane and/or n-octane to isoheptanes, iso-octanes,butane and iso-butane, methylcyclopentane to cyclohexane, meta-xyleneand/or ortho-xylene to paraxylene, 1-butene to 2-butene and/orisobutene, n-hexene to iso-hexene, cyclohexene to methylcyclopenteneetc.

Catalyst compositions comprising UZM-53 may be particularly useful forthe oligomerization of olefins to longer olefins such as gasoline anddistillate range olefins. Light olefins such as ethene, propene, buteneand pentenes may be oligomerized to gasoline or distillate rangeolefins. Liquid phase operation is typically preferred. Operatingpressures may include between about 2.1 MPa (300 psia) and about 10.5MPa (1520 psia), but other pressures are contemplated depending on feedand recycle such that liquid phase is maintained. With liquidoligomerate recycle, lower pressures are often possible to maintainliquid phase. Temperature may be in a range between about 100° C. andabout 350° C. or may be between about 180° C. and about 300° C. Theweight hourly space velocity may be between about 0.5 and about 10 hr⁻¹.Additional conditions for successful operation may be given in U.S. Pat.No. 9,278,893, hereby incorporated by reference.

The proton (W) form of UZM-53 may additionally be characterized byinfrared spectroscopy coupled with probe molecules. Ammonia is capableof accessing all acid sites in a MTT zeolite comprising 10-membered ringpores. Adsorbed NH₃ coordinates with both Brönsted and Lewis acid sites.A distinct infrared absorbance band is observed for both types of acidsites. The integrated band area gives a relative measure of total numberof acid sites. Discrete desorption experiments provide a relativemeasure of acid site strength. UZM-53 possesses only small amounts ofLewis acid sites. In an embodiment, the NH₃ Lewis acid value may be lessthan 0.05 or may be less than 0.04 or may be less than 0.03. UZM-53possesses large quantities of Brønsted acid sites. In an embodiment, theNH₃ Brønsted value may be greater than 3.00 or may be greater than 4.00or may be greater than 4.50 or may be greater than 5.00. Collidineadsorption experiments performed in analogous manner yield equivalentinformation on the external Brönsted acidity of catalyst materials.Collidine (2,4,6-trimethylpyridine) is too large to enter the10-membered ring of MTT zeolites. UZM-53 possesses only small amounts ofexternal Bronsted acidity. In an embodiment, the Collidine Brønstedvalue may be less than 0.12 or may be less than 0.10.

The invention will now be further illustrated by the followingnon-limiting examples.

Example 1

Of sodium hydroxide (99% purity), 0.675 g were weighed into a 250 ccTeflon beaker and 1.085 g potassium hydroxide (87.3% purity) was added.Then, 55.9 g water and a stir bar were added and stirring started. Whenthis became a clear solution, 2.43 g aluminum hydroxide (27.9% Al byanalysis) was added. When this became a clear solution 42.69 g of a 50%aqueous solution of diisopropanolamine was added. Next, 4.14 gtetramethyl-1,3propanediamine (99+% purity) was added. Finally, 75 gLudoxAS-40 was slowly added. This became a thin, pourable gel. The gelwas transferred to a 300 cc stirred autoclave and digested at 175° for120 hours at 250 rpm.

The solid product was recovered by filtration, washed with de-ionizedwater and dried at 95° C. The resulting product was identified to beUZM-53 by XRD and is shown in FIG. 1. The composition of the productconsisted of the following mole ratios: Si/Al=18.14, Na/Al=0.105,K/Al=0.195, N/Al=1.125, and C/N=3.75. This material was then calcinedunder air at 600° for 12 hours. Surface area analysis showed a BET SA of178 m²/g, total pore volume of 0.166 mL/g and a micropore volume of0.081 mL/g. The XRD of the calcined material is shown in FIG. 2. Aportion was then ion-exchanged four times with ammonium nitrate at 75°C. for an hour each time before activation at 500° C. for 2 hours in airto yield the H⁺ form. In FIGS. 1 and 2, Two-Theta (deg) is on the x-axisand Intensity (Counts) on the y-axis.

Example 2

Of sodium hydroxide (99% purity), 0.44 g were weighed into a 250 ccTeflon beaker and 0.74 g potassium hydroxide (87.3% purity) was added.Then, 51.5 g water and a stir bar were added and stirring started. Whenthis became a clear solution, 1.62 g aluminum hydroxide (27.9% Al byanalysis) was added. When this became a clear solution 14.28 gdiisopropanolamine (98% purity) was added. Next, 2.76 gtetramethyl-1,3propanediamine (99+% purity) was added. Finally, 50 gLudoxAS-40 was slowly added. This became a thin, pourable gel. Thereaction mixture with Si/Al=20 was transferred equally to 4 45 mLautoclaves and digested at 175° while tumbling at 15 rpm in a rotisserieoven for 4, 5, 6, and 7 days, respectively.

The solid products were recovered by filtration, washed with de-ionizedwater and dried at 95° C. The product resulting from all reactions wereidentified to be UZM-53 by XRD, with the 4 day material still containingsome amorphous product. The composition of the product from the 5 daysynthesis consisted of the following mole ratios: Si/Al=19.34,Na/Al=0.064, K/Al=0.17, N/Al=1.31, and C/N=3.60. This material was thencalcined under air at 600° for 18 hours. Surface area analysis showed aBET surface area of 178 m²/g, total pore volume of 0.157 mL/g and amicropore volume of 0.084 mL/g.

Comparative Example 3

Of sodium hydroxide (99% purity), 0.47 g were weighed into a 250 ccTeflon beaker and 0.71 g potassium hydroxide (87.3% purity) was added.Then, 51.5 g water and a stir bar were added and stirring started. Whenthis became a clear solution, 1.08 g aluminum hydroxide (27.9% Al byanalysis) was added. When this became a clear solution 14.35 gdiisopropanolamine (98% purity) was added. Finally, 50 g LudoxAS-40 wasslowly added. This became a thin, pourable gel. The reaction mixture ofSi/Al=30.5 was transferred equally to 4 45 mL autoclaves and digested at175° while tumbling at 15 rpm in a rotisserie oven for 4, 5, 6, and 7days, respectively.

The solid products were recovered by filtration, washed with de-ionizedwater and dried at 95° C. The product resulting from all reactions wereidentified to be MTT by XRD, with the 5 and 6 day materials containingsome cristobalite. At 76 hours, this same reaction mixture had beenamorphous in a previous experiment. The composition of the product fromthe 4 day synthesis consisted of the following mole ratios: Si/Al=26.8,Na/Al=0.13, K/Al=0.37, N/Al=0.76, and C/N=5.63. The XRD of the materialis shown in FIG. 3. Two peaks of very strong intensity and 4 peaks ofstrong intensity are present.

Comparative Example 4

Of sodium hydroxide (99% purity), 0.48 g were weighed into a 250 ccTeflon beaker and 0.71 g potassium hydroxide (87.3% purity) was added.Then, 51.5 g water and a stir bar were added and stirring started. Whenthis became a clear solution, 1.24 g aluminum hydroxide (27.9% Al byanalysis) was added. When this became a clear solution 14.23 gdiisopropanolamine (98% purity) was added. Finally, 50 g LudoxAS-40 wasslowly added. This became a thin, pourable gel. The reaction mixture ofSi/Al=26 was transferred equally to 4 45 mL autoclaves and digested at175° while tumbling at 15 rpm in a rotisserie oven for 4, 5, 6, and 7days, respectively. The solid products were recovered by filtration,washed with de-ionized water and dried at 95° C. The product resultingfrom all reactions were largely amorphous by XRD.

Example 5

Of sodium hydroxide (99% purity), 0.48 g were weighed into a 250 ccTeflon beaker and 0.73 g potassium hydroxide (87.3% purity) was added.Then, 51.5 g water and a stir bar were added and stirring started. Whenthis became a clear solution, 1.62 g aluminum hydroxide (27.9% Al byanalysis) was added. When this became a clear solution, 14.39 gdiisopropanolamine (98% purity) was added. Next, 1.38 gtetramethyl-1,3propanediamine (99+% purity) was added. Finally, 50 gLudoxAS-40 was slowly added. This became a thin, pourable gel. A portionof the gel was analyzed for flammability and found to have a 80° C.flashpoint. The remaining gel was transferred equally to 5 45 mLautoclaves and 4 digested at 175° while tumbling at 15 rpm in arotisserie oven for 5, 6, 7, and 8 days, respectively, while 1 washeated statically at 175° C. for 6 days.

The solid products were recovered by filtration, washed with de-ionizedwater and dried at 95° C. The product resulting from the reaction wasidentified to be UZM-53 by XRD. The composition of the product from the5 day synthesis consisted of the following mole ratios: Si/Al=19.4,Na/Al=0.11, K/Al=0.23, N/Al=1.13, and C/N=3.92.

Example 6

Liquid sodium aluminate and liquid potassium aluminate were combinedwhile stirring. Diisopropanolamine was then added. Next,tetramethyl-1,3propanediamine (99+% purity) was added. Finally,LudoxAS-40 was slowly added. This became a thin, pourable gel ofcomposition 1 Al₂O₃:40 SiO₂:0.68 Na₂O:0.66 K₂O:12.5 DIPA:2.53 TMPDA:542H₂O. The gel was transferred to a 2 L autoclave and digested at 175°while stirring at 300 rpm for 144 hours.

The solid products were recovered by filtration, washed with de-ionizedwater and dried at 95° C. The product resulting from the reaction wasidentified to be UZM-53 by XRD and is shown in FIG. 4. A portion of themother liquor from the filtration was saved before washing and analyzedby ¹³C NMR, which is shown in FIG. 5. Six peaks of approximatelyequivalent intensity were observed for diisopropanolamine and threepeaks in a 1:4:2 ratio were observed for tetramethylpropanediamine. Themolar ratio of diisopropanolamine to tetramethylpropanediamine was about11.5.

Peak Location (ppm) Integral 20.12 15.2 20.20 15.2 23.91 1.2 43.72 5.355.46 14.7 55.72 15.2 56.40 2.7 66.15 14.9 66.41 15.2

Another portion of the mother liquor was analyzed for flash point andfound to have a flash point of >90° C. The composition of the productconsisted of the following mole ratios: Si/Al=18.9, Na/Al=0.069,K/Al=0.18, N/Al=1.26, and C/N=3.77. This material was then calcinedunder air at 600° C. for 12 hours. The XRD pattern of the calcinedUZM-53 is shown in FIG. 6. The product was then ion-exchanged threetimes with NH₄NO₃ and calcined at 550° C. for 3 hours to yield the H⁺form. An SEM photo at 100 nm range is shown in FIG. 7.

Example 7

Liquid sodium aluminate and liquid potassium aluminate were combinedwhile stirring. Sodium chloride and potassium chloride were then added.Diisopropanolamine was then added. Next, tetramethyl-1,3propanediamine(99+% purity) was added. Finally, LudoxAS-40 was slowly added. Thisbecame a thin, pourable gel of composition 1 Al₂O₃:40 SiO₂:0.68Na₂O:2.96 NaCl:2.96 KCl:0.66 K₂O:12.5 DIPA:0.32TMPDA:543 H₂O. Of thegel, 831 g was transferred to a 2 L autoclave and digested at 175° C.while stirring at 300 rpm for 119 hours. The solid products wererecovered by filtration, washed with de-ionized water and dried at 95°C. 157 g product were recovered. The product resulting from the reactionwas identified to be UZM-53 by XRD. The composition of the productconsisted of the following mole ratios: Si/Al=19.4, Na/Al=0.07,K/Al=0.53, N/Al=0.59, and C/N=5.04.

Example 8

In the present invention, the presence of Brönsted and Lewis acid siteswere determined by infrared spectroscopy using the following standardprocedures. All procedures started with sample preparation andactivation. The samples were ground and pressed into self-supportingpellets. Pretreatment of samples was performed in-situ in UHP 20% O₂/N₂gas flow at 500° C. for 2 hours to remove water. Gas flow was switchedto He and the sample was cooled to room temperature and the hydroxylspectrum was recorded.

Total acidity determination: The sample was heated to 150° C. and onceat this temperature; 1% NH₃ in UHP He was flowed over the sample for 10minutes followed by equilibration of the sample for an additional 50minutes. Samples were cooled to room temperature and excess NH₃ waspurged in He flow. Desorption experiments were performed by heating thesample in He flow to 150° C. holding at temperature for 1 hour thencooling to room temperature and recording a spectrum. The pretreatedspectrum was subtracted from each desorption spectra and the Brönstedand/or Lewis acid site adsorbed absorbance bands integrated to determinethe relative total acidity of the materials. The value of the Lewis acidpeak divided by the sample mass gives the NH₃ Lewis acid value(area/mg). The value of the Brønsted peak divided by the sample massgives the NH₃ Brønsted acid value (area/mg).

The external Brönsted acidity determination: The sample is heated to150° C. and once at temperature He saturated with collidine at 7° C. isflowed over the sample for 10 minutes followed by equilibration of thesample for an additional 50 minutes. Sample is cooled to roomtemperature and excess collidine is purged with He flow. Desorptionexperiments are performed by heating the sample in He flow to 150° C.holding at temperature for 1 hour then cooling to room temperature andrecording a spectrum. The pretreated spectrum was subtracted from thedesorption spectra and Brönsted acid site adsorbed absorbance bands wereintegrated to determine the Collidine Brønsted value per milligram ofthe materials (area/mg).

In addition to materials described in the examples, a sample of MTTzeolite from Zeolyst was purchased which had Si/Al=23. All materialswere tested in H⁺ form.

Table of Data Collidine NH₃ NH₃ Sample Brønsted Lewis Brønsted ZeolystMTT 0.25 0.021 4.98 Example 6 0.12 0.04 5.33 COMP Example 9 0.22 0.0522.42 Example 1 0.10 0.027 4.88 Repeat Example 1 0.10 0.031 4.99

Comparative Example 9

Example 1 of U.S. Pat. No. 4,076,842 was repeated. Twice the amount ofreaction mixture was created to allow analysis for flammability. Thereaction mixture had a flashpoint of 49.5° C. The solid products wererecovered by filtration, washed with de-ionized water and dried at 95°C. The product resulting from the reaction after 4 or 6 days wasidentified to be ZSM-23 by XRD.

Comparative Example 10

Isobutylamine was utilized as the organic structure directing agent forpreparation of a MTT zeolite from a mixture of composition 45SiO₂:Al:5.50 NaOH:9 iBuNH₂:834 H₂O Weighed 223.88 g deionized water intoa large beaker and, with overhead stirring added 4.73 g NaOH pellets.Clear solution in ˜5 min. Added 123.89 g Ludox AS40 while mixing. Now anopaque solution. Added 33.34 g of Nalco 1056 (1.74% Al, 12.0% Si, 0.026%Na). Mixed for 15 min after the addition of the Nalco sol. Still a thinwhite solution. Added 14.15 g isobutylamine (99% Aldrich) dropwise,stirred 5-7 minutes. Thin translucent white liquid, pH=12.80 A portionof this liquid was analyzed for flammability and determined to have aflashpoint of 35° C. The remaining gel was then split into 2 and ˜197 gloaded into separate 300 cc reactors. Both stirred autoclaves wereramped to 150° C. in 8 h. Reactor A was held at 150° C. for 48 h, whileReactor B was held at 150° C. for 120 h. An anchor-type stirrer was usedwith a setting of 250 rpm. After 2 days, reactor A was worked up. Theproduct was a mixture of thin, white liquid and thick, white paste withpH=10.71. The product was centrifuged at 10,000 RPM and washed withwater then dried at 100° C. Yield: 25.68 g. Analytical results showed2.88 wt % C, 0.84 wt % N, 45.2 wt % Si, 1.07 wt % Al and 1 wt % Na.

Example 11

The calcined form of the Example 6 UZM-53 material was ion-exchanged tothe H+ form and then extruded as ⅛″ cylinders in a 25% UZM-53/75% Al₂O₃formulation, dried at 110° C. overnight and then calcined to 550° C. togive the UZM-53/Al₂O₃ catalyst. The feed for the oligomerizationexperiment was as shown in Table 1. The oligomerization feed wascontacted with the UZM-53 catalyst at 900 psig, 1.5 WHSV at a range ofweight average bed temperatures from 200-230° C. after a break-in periodof 75 hours at 0.75 and 1.5 WHSV to yield the results shown in Table 2and FIG. 6. The UZM-53 catalyst is active and selective in convertinglight olefins to distillate range product. In FIG. 6, total C4 olefinconversion in weight percent is indicated in gray diamonds with blackoutline, selectivity to C8-C11 compounds in gray circles with blackoutline and dashed trend line, selectivity to C12-C15 compounds in graytriangles with black outlines and selectivity to C16+ compounds in blackGreek crosses.

TABLE 1 Component wt % C3 0.037 C3═ 0.172 iC4 69.276 nC4 0.093 iC4═7.854 1-C4═ 5.885 2-C4═ 16.516 C5═ 0.167

C4= nC4= iC4= C5-C7 C8-C11 C12-C15 C16+ HOS WABT conversion conversionconversion selectivity selectivity selectivity selectivity 76 201 68.6768.95 64.51 2.12 42.72 38.11 17.05 90 211 73.68 73.73 70.70 2.40 41.6239.61 16.37 91 211 74.04 74.05 71.21 2.44 41.32 39.56 16.67 111 22077.88 77.69 76.02 2.44 34.46 42.11 20.99 112 220 77.84 77.64 75.97 2.3132.00 42.16 23.53 150 230 81.60 81.26 80.55 3.18 32.79 42.67 21.36 151230 89.46 92.29 80.47 3.16 32.49 42.62 21.73 194 230 75.65 76.24 73.954.24 36.03 41.74 17.99 195 229 75.39 75.97 73.71 4.20 36.19 41.62 18.00270 229 68.51 69.34 66.15 4.49 42.02 39.09 14.41 271 229 68.74 69.5566.43 4.53 40.68 37.61 17.17

The invention claimed is:
 1. A hydrocarbon conversion process comprisingcontacting an olefin with a catalyst at oligomerization conditions toconvert the olefin to a product comprising longer olefins, the catalystcomprising a microporous crystalline zeolite having a three-dimensionalframework of at least AlO₂ and SiO₂ tetrahedral units and an empiricalcomposition in an as synthesized and anhydrous basis expressed by anempirical formula of:M⁺ _(m)R_(r)Al_(1-x)E_(x)Si_(y)O_(z) where M represents sodium,potassium or a combination of sodium and potassium exchangeable cations,“m” is the mole ratio of M to (Al+E) and varies from about 0.05 to about1, R is the organic structure directing agent or agents derived fromreactants R1 and R2 where R1 is diisopropanolamine and R2 is a chelatingdiamine, “r” is the mole ratio of N from the organic structure directingagent or agents to (Al+E) and has a value of from about 0.4 to about1.5, E is an element selected from the group consisting of gallium,iron, boron and mixtures thereof, “x” is the mole fraction of E and hasa value from 0 to about 1.0, “y” is the mole ratio of Si to (Al+E) andvaries from greater than 12 to about 30 and “z” is the mole ratio of Oto (Al+E) and has a value determined by the equation: z=(m+3+4·y)/2 andis characterized in that it has the x-ray diffraction pattern having atleast the d-spacing's and intensities set forth in Table A: TABLE A 2θd(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.38 7.77 M 15.91 5.56 W 16.325.43 W 18.18 4.88 W—M 19.72 4.50 S 20.04 4.43 W—M 21.00 4.23 S 21.504.13 W—M 22.90 3.88 VS 24.10 3.69 VS 24.62 3.61 S 25.34 3.51 M—S 26.023.42 W 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52  M—S.


2. The process of claim 1 wherein said microporous crystalline zeolitehas a y in said empirical formula that is less than
 25. 3. The processof claim 1 wherein said microporous crystalline zeolite has a y in saidempirical formula that is less than
 22. 4. A hydrocarbon conversionprocess comprising contacting an olefin with a catalyst atoligomerization conditions to convert the olefin to a product comprisinglonger olefins, the catalyst comprising a microporous crystallinezeolite having a three-dimensional framework of at least AlO₂ and SiO₂tetrahedral units and an empirical composition in the hydrogen formexpressed by an empirical formula ofM1_(a)′N⁺Al_((1-x′))E_(x′)Si_(y′)O_(z)— where M1 is at least oneexchangeable cation selected from the group consisting of alkali,alkaline earth metals, rare earth metals, ammonium ion, hydrogen ion andcombinations thereof, “a′” is the mole ratio of M1 to (Al+E) and variesfrom about 0.05 to about 1, “N” is the weighted average valence of M1and has a value of about +1 to about +3, E is an element selected fromthe group consisting of gallium, iron, boron, and combinations thereof,x′ is the mole fraction of E and varies from 0 to 1.0, y′ is the moleratio of Si to (Al+E) and varies from greater than about 12 to about 30and z″ is the mole ratio of 0 to (Al+E) and has a value determined bythe equation:z″=(a·N+3+4·y′)/2 and is characterized in that it has the x-raydiffraction pattern having at least the d-spacing's and intensities setforth in Table B: TABLE B 2θ d(Å) I/I₀ % 8.02 11.0 M 8.92 9.91 W—M 11.387.77 M 15.91 5.56 W 16.32 5.43 W 18.18 4.88 W 19.72 4.50 VS 20.04 4.43W—M 21.00 4.23 S 21.50 4.13 W 22.90 3.88 S 24.10 3.69 S 24.62 3.61 M25.34 3.51 M 26.02 3.42 M 28.30 3.15 W—M 31.62 2.83 W—M 35.60 2.52  M.


5. The process of claim 4 wherein in the empirical formula for saidmicroporous crystalline zeolite, y′ is from about 12 to
 25. 6. Theprocess of claim 4 wherein said microporous crystalline zeolite has aNH₃ Lewis acid value of less than 0.05.
 7. The process of claim 4wherein said microporous crystalline zeolite has a NH₃ Lewis acid valueof less than 0.04.
 8. The process of claim 4 wherein said microporouscrystalline zeolite has a NH₃ Lewis acid value of less than 0.03.
 9. Theprocess of claim 4 wherein said microporous crystalline zeolite has aCollidine Brønsted value of less than 0.12.
 10. The process of claim 4wherein said microporous crystalline zeolite has a Collidine Brønstedvalue of less than 0.1.
 11. The process of claim 4 wherein saidmicroporous crystalline zeolite has a micropore volume as a percentageof total pore volume of less than 70% as determined by BET analysisusing N₂.
 12. The process of claim 4 wherein said hydrocarbon conversionconditions comprise a pressure between about 2.1 MPa and about 10.5 MPa,a temperature between about 100° C. and about 350° C. and a weighthourly space velocity between about 0.5 and about 10 hr⁻¹.
 13. Theprocess of claim 4 wherein M1 comprises a combination of sodium andpotassium cations and the molar ratio of Na/K in M1 is in the range from0.10 to
 2. 14. The process of claim 4 wherein said x-ray diffractionpattern comprises only one peak of very strong intensity.